Hydrocarbon conversion process



Nov. 15, 1949 EVANS 2,487,795

HYDROCARBON CONVERSION PROCESS Filed Dec. 20, 1947 HOPPER 43 8 COOLERHOPPER 4ND 70 HEATER 6 ON VE ran J 3 our SPF/V7 was SOLVE/VT hF/MES 3eauue'r REMOVAL CONVERTOR PRODUCT REC OVER! SYSTEM /09 IOIV SUPPOR TIA 65A5 IN I N V EN TOR. 1.00/5 P EVA/V5 AGE/V7 0/? ATTORNEY Patented Nov.15, 1949 HYDROCARBON CONVERSION PROCESS .Louis P. Evans, Woodbury, N.J., assignor. to Socony-Vacuum Oil Company, Incorporated, a corporationof New York Application December 20, 1947, Serial No. 793,000

. 1 This invention pertains to a process for conversion of high boilinghydrocarbons at controlled elevated temperatures in the presence of aparticle-form contact mass material. This invention is particularlyconcerned with a process for the conversion of hydrocarbon feed stockswhich contain both asphaltic and oily constituents.

Such conversion processes may involve treating, reforming,polymerization, oxidation, desulphurizatidn, cracking, etc., of thehydrocarbons. A particularly important process is the catalytic crackingconversion of hydrocarbons, it being well known, for example, thathydrocarbon fractions boiling above the gasoline boiling range may beconverted to lower boiling gasoline containing hydrocarbons upon beingsubjected to contact with a suitable solid porous catalyst at 8 Claims.(01. 196-52) temperatures of the order of 800 F. and upwards and atpressures usually above atmospheric.

Heretoiore, such conversion processes have been limited to theconversion of a relatively light, clean, substantially tar or asphaltfree pctroleum feed stocks because of the tendency of the asphaltcontaining stocks to cause the formation .of excessive deposits of cokycontaminants on the catalyst which deposits cannot be economicallyremoved. In order to avoid these heavy coke deposits which render thecracking process unfeasible, it has been the wide refinery practice tosubject some high boiling petroleum feed stocks (when available with abroad boiling range) to'a preliminary tar separation step, separate aneasily vaporizable fraction from a liquid fraction which bears theasphaltic constituents and to subject only the vaporizable fraction tocatalytic cracking while discarding the liquid tar separator bottoms.Since this discarded fraction may be made up. of a large proportion ofvaluable oily constituents and a smaller proportion of asphalticconstituents, it is obvious that a large quantity of otherwiseacceptable catalytic cracking feed stock is lost and unavailable as suchin the prior art tar separator operation. When the crude residuum is notof such boiling range and does not contain substantial amounts ofvaporiz-- able gas oil, it has been considered in practice as beingunsuitable as such for a cracking charge stock. The problem is becomingincreasingly serious due to the fact that relatively low boilingpetroleum crudes are becoming less plentiful and the crudes which aremost readily available are high boiling crudes in which the oilyconstituents boil so high as to prevent their separation from asphalticconstituents by distillation process without subjecting them totemperatures at which undesirable thermal cracking and excessive cokingoccur. As a result, in order to use such high boiling stocks at all, itis necessary first to subject them to a preliminary thermal coking stepto provide some lower boiling oily fractions for a subsequent catalyticcracking operation. By-products from the coking process are a heavyliquid out which may contain a substantial amount of oily constituentsas well as asphaltic constituents and a very large amount of petroleumcoke, the disposal of which often creates a serious refinery problem.

A novel process for conversion of high boiling hydrocarbons whichovercomes th above difilculties is described and broadly claimed in mycopending application Serial Number 720,271 tiled in the United StatesPatent Ofiice, January 4:, 1947, now abandoned. In that application theprocess described is broadly one wherein the by drocarbon feed fractionbearing asphalt and oily constituents is contacted under suitablesorption conditions with a particle-form porous contact material whichis suitable for sorbing the oily constituents of the feed in the poresof the contact material while leaving substantially un sorbed theasphaltic constituents of the liquid feed. A substantial separation ofunsorbed asphaltic constituents from the contact material bearing sorbedoily constituents is then efiected. The separated contact materialbearing sorbed oily constituents is then heated to a temperaturesuitable for effecting the desired conversion of the sorbed oilyconstituents. The present inven-- tion deals specifically with animprovement in the above described process wherein the contact materialbearing sorbed oily constituents is heated to a temperature suitable forconversion of the sorbed hydrocarbons by contacting it directly with aliquid heat exchange fluid such as a molten metallic alloy. The contactmaterial after sepa ration from the gaseous hydrocarbon conversionproducts and after separation from the liquid heat exchange fluid issubjected to regeneration to prepare it for reuse.

A major object of this invention is the provision of a process forconversion of the oily constituents in high boiling asphalt bearinghydrocarbon fractions without the formation of prohibitive amounts ofcoke.

A specific object of this invention is the provislon in a processwherein oily constituents from asphalt bearing petroleum fractions aresorbed on a. suitable porous sorbent, and then converted at highertemperatures in the presence of the sorbent and in the absence oi theasphalt constituents of the petroleum fraction of an improved method forchanging and controlling the solvent temperature during the conversionoperation.

The size or the sorbent particles employed in the process or thisinvention is to some extent dependent upon the. variables involved inany particular application of the process. These im- These and otherobjects of this invention'will portant variables are time or contactbetween the liquid asphalt bearing charge and the sorbent in thesorption zone, temperature in the sorption zone, viscosity or the liquidcharge. and to a lesser extent the ratio-0f liquid oil to sorbentcharged to the sorption zone. Increasing time of contact and increasingtemperature result in a decrease in the emciency of separation ofasphaltic and oily constituents. Decreasing viscosity of the liquidcharge has the same effect. On the other hand increasing temperatureanddecreasing viscosity both result in more rapid sorption of thepercolation of the oils through clay-type adsorb-' ents. The presentprocess is the opposite of the so-called percolation and contactfiltration processes for oil refining in that, by the present process,it is the oily constituent and not the asphaltic constituent which issorbed by the contact material. This fundamental diflerence makespossible the combination cracking process of this invention and permitsthe elimination of the asphalt materials without contamination of thecatalyst thereby. It has been found that porous con tact materials,having a structure corresponding to that of an inorganic oxide gelhaving a subliquid oily constituents by the sorbent. If the ratio orsorbent to liquid charge is excessive some loss in separation eiliciencyresults. By proper control of these variables some latitude in theaverage diameter or the sorbent employed may be provided. However whenthe diameter of the particles becomes too small, the sorbentpreferentially adsorbs the asphaltic constituents from the liquid chargein the same manner as well known oil filtering clays. This is shown inTable I below in which is tabulated the deasphalting results obtained onMid-Continent residuums using a silicaalumina gel type sorbent having a'bulk density in the 4-8 mesh size range of about 0.7.

Table 1 Experiment Number l 4 5 6 7 2 3 Charge Viscosity, S. U. V 116.9116. 9 81. 8 81. 8 81.8 81.8 340 Charge. Ramsbottom Carbon. 2.3 2. 3 2.32.3 6.1 Mesh Size of Borbent ('gylerL. 30-60 30-60 60-8) 31-60 4-8 4-8sorption Zone Contact ime... 24 hrs. 24 hrs. 2 min. 2 min. 2 hrs. 72hrs. 4 his. BOIFHOD Zone, Temperature F... 160 150 150 150 150 75 276 Weght Ratio of Borbent to lliquid Charge 1 1 l 1 1 1 2.2 Properties ofOily Constituents Retained by Borbent alter Washing: v

S, U. 210 F. Sec 09.7 129.2 75.2 81.7 115.4 49.7 161 Ramsbottom Carbon,Per Cent- 1. 8 2. 3 3. l 2. 4 Properties of Materials Washed iromSorbent Surface:

B. U. V. 210 F. 860 164 100. 1 85. 9 80.5 76.0 139. 2 660 RamsbottomCarbon, Per Cent 2. 4 2. 2 2. 0 3. 6 6. 7

stantially uniform porosity of low macropore volume with an average pordiameter not exceeding about 125 Angstrom units and a particle sizepreferably larger than that corresponding to about 30 mesh (Tyler) havethe ability to sorb the oily constituents of a liquid hydrocarbontraction while leaving substantially unsorbed the asphalticconstituents. Natural and treated clays and bauxites such as areemployed in oil filtering and decolorizing processes do not appear tohave this property. The macropore volume of the contact materialemployed in the present invention should be relatively low so that thepore volume is mostly that or micropores. In general, the volume ofmacropores, that is. those pores having radii larger than 100 Angstromunits, should constitute less than about 30 percent of the total porevolume and preferably 10 percent or less. The measurement oi pore sizeand pore size distribution in various porous materials is discussed indetail by L. C. Drake and H. L. Bitter in Industrial and EngineeringChemistry, Analytical Edition, volume 17, pages 782-791, 1945. Themethods described there were essentiall those employed in determiningthe bulk densities, aver. age pore diameters, andother pore measurements01' the adsorbents employed in the present invention.

when the contact periodwas 24 hours (Experiment 4) or even 2 hours(Experiment 7 the sorbent acted similar to a normal filtering clay andpreferentially adsorbed the asphaltic constituents. But when the contacttime was reduced to two minutes (Experiment 5) the 30-60 mesh sorbentexhibited a preference for the oily constituents over the asphalticconstituents.

When particle size was reduced below 60 mesh,

the sorbent preferentially adsorbed the asphaltic constituents even atvery low contact periods (Experiment 6).

The effect of' contact time and temperature is shown in Table II belowin which are presented the deasphalting results on an East Texasresiduum having an original Saybolt Universal viscosity of 512 secondsat 210 F. and a Ramsbottom carbon residue of 11.1. In this experimeat asilica-alumina gel type sorbent of 4-8 mesh size and 0.48 bulk densitywas employed.

In general it may be said that the particle size of the sorbent materialparticularly in the case of inorganic oxide gel type sorbents should begreater than that corresponding to about 60 mesh Tyler and preferablywithin the range about 0.022 to 1.0 inches average diameter, The

size ranges given although the results will be less satisfactory. It iscontemplated that in its broader aspects this invention covers theselatter operations as well as the operations within the specifiedpreferred limits.

The porosity of the gel particles employed in the process of thisinvention is of fundamental importance. The degree of. porosity isgenerally reflected in the bulk density of the gel composite used; thelower the bulk density, the greater being the degree of porosity. Forthe purposes of the present process, porous sorbent particles havingbulk densities of between about 0.4 and 1.1 gram per cubic centimeterare preferred. The bulk densities indicated correspond to an averagepore diameter of between about 20 and about 125 Angstrom units.Preferably, the sorbent used will have a bull; density between about 0.6and about 0.8 gram per cubic centimeter. Gel particles having a bulkdensity greater than about 0.8 have been found to have excellentselectivity but poor sorbing capacity, while particles with a bulkdensity less than about 0.6 have relatively poor selectivity. However,since the selectivity of the deasphalting process improves with adecrease in temperature, particles with a bulk density less than 0.6would be satisfactory for deasphalting stocks which can be processed atlow temperatures.

The degree of porosity of a synthetic inorganic oxide gel will, ingeneral, depend on the conditions under which it is prepared and allowedto set to gelation. A particularly convenient method of preparing gelparticles used in the process of this invention is described in U. S.2,384,946, issued September 18, 1945, to Milton M. Marisic. It is theredisclosed that spheroidal particles of inorganic oxide gel may beprepared by mixing an acidic stream of sodium silicate and allowing theresulting sol to be ejected from a nozzle into an oil column, where thegel sets in the form of bead-like spheroids. The resulting gel spheres,after washing, drying and tempering, were of a size varying betweenabout 4 and about 20 mesh. The gel beads so produced had a bulk densityof between about 0.4 and about 1.1 and an average pore diameter ofbetween about 20 and about 125 Angstrom units. They proved to beexcellent selective absorbents Ior use in the process of this invention.

Likewise, irregularly shaped porous absorbent fragments or particleshaving the structure of inorganic oxide gels may be used. However, ingeneral, spheroidal particles are to be preferred, since attritionlosses are then at a minimum and contamination with gel fines of theasphalt-bearing stock is substantially eliminated.

In general, siliceous gel particles will be used in the process of thisinvention, such as silica gel, silica-alumina gel, silica-zirconia gel,silicathoria gel, silica-magnesium oxide gel and the like. Poroussorptive silica glasses having a structure approaching that of asiliceous gel likewise are contemplated for use in the processdescrlbed'herein, it being necessary, however, that the porous glassesemployed have an average pore diameter less than about Angstrom units,and a macropore volume of less than about 30 percent of the total porevolume.. The size of the porous glass particles must also be carefullycontrolled so as to obtain preferential sorption of the oilyconstituents. Usually particles of less than 60 mesh size areundesirable. It is also contemplated that within the scope of thisinvention other porous materials not of the inorganic oxide gelcomposition which have structures approaching that of a siliceous geland are within the above specified pore size and particle size limitsmay be employed within the scope of this invention.

Typical of the porous glasses used are those described in U. S.2,106,744, issued February 1, 1938, to Hood et al. There it is disclosedthat a silica-alkali-borlc oxide glass of suitable compositlon isprepared by a fusion process. Heat treatment of this glass results inseparation of the glass into two phases; one phase is rich inalkaliboric oxide and is soluble in acids, while the other phase, whichis insoluble in acid, consists of silica with a small amount of boricoxide. Extraction of this heat treated glass with acid results in aporous silica glass which can be employed as a porous absorbentseparating medium in accordance with the present invention.

The liquid heat exchange fluid employed in this invention may be asuitable inorganic salt melt or preferably a molten metal or metallicalloy having a boiling point substantially above the highest temperatureat which it is employed in the process and having a melting pointsubstantially below the desired hydrocarbon conversion temperature. Theheat exchange fluid should be oxygen-insensitive and should have asumciently high surface tension to avoid appreciable wetting of thecontact material involved. It will be apparent that the proper choice ofthe heat exchange liquid will be dependent upon the particularconversion conditions and catalyst material involved in any givenapplication of the invention. As an example, where the reaction involvedis a catalytic cracking conversion of hydrocarbons occurring attemperatures of the order of 800-1000 F., molten lead orzinc may beemployed or some metallic alloy having a melting point below about 750F.- 800 F. and having a low vapor pressure at 10001100 F. An example ofsuch an alloy is one consisting of 50 percent lead and 50 percent sodiumwhich has a melting point of about 627 F. Exemplary of inorganic saltmelts which may be employed when the reaction involved is catalyticcracking is cuprous chloride melting at about 788 F. The melting pointof this salt melt may be reduced by the addition of alkali metalchloride in small amounts. For higher temperature reactions a suitablefluid is a mixture of 50 percent lithium sulphate and the balance ofapproximately equal parts of the sulphates of sodium and manganese,which mixture melts at about 875 F. When the reaction involved is a lowtemperature treatment or molecular rearrangement of the sorbedhydrocarbons, a low melting point alloy'may be employed such as amixture of 50 percent tin and 50 percent lead melting at about 429 F.

The invention may be most readily understood by reference to theattacheddrawing which is a schematic arrangement of the system of thisinvention in which the apparatus is shown partially in section. In thedrawing, vessel 20 is a deasphalting chamber which may be of rectangularor any other desired cross-sectional shape. A partition 24 across theupper section of chamber 20 defines a solid inlet surge chamber 25 inits upper end. Tubes 26 depend from partition 24 for flow of contactmaterial from chamber 25 onto the surface of the substantially compactcontact material column maintained in the sorption section 28 of thedeasphalting vessel. Particle form contact material having a catalytic.

activity for the desired conversion and being suitable for sorbing theoily constituents of a liquid feed while leaving substantially unsorbedthe asphalt constituents thereof is cooled to a suitable temperature inhopper 29 positioned above vessel 20 and then passed via conduit 2| intovessel 20 to keep replenished the column of such material in section 28of vessel 20. -A hydrocarbon feed stock which contains both asphalticand oily constituents, for example a heavy petroleum residuum fractionor a tar separator bottoms fraction, is introduced into chamber 20 frommanifold In via headers I l, closed on their ends, which extend intospace 30 and nozzles l2 which are spaced along headers II. The liquidcharge distributes itself over the surface 21 of the contact materialcolumn and percolates downwardly within the column, whereby the oilyconstituents become sorbed in the pores of the contact material and theasphalt constituents remain substantially unsorbed. The contact materialbearing sorbed oily constituents and the unsorbed liquid are withdrawntogether from the bottom of vessel 20 through duct 22 at a suitable ratecontrolled by the valve 3|.

The mixed liquid and solid material are directed by duct 22 onto anendless foraminous moving belt l4 supported over horizontally spacedpulleys l5 and IS, the latter of which is rotated by means of drivemotor H. The drain duct 22 and valve 3| therein may extend horizontallysubstantially the width of belt l4 so as to uniformly distribute solidmaterial and liquid across the belt. Suitable guards (not shown) may beprovided within chamber 35 along the opposite sides of the belt I4 toprevent solid particles from falling off the sides. A drain pan i8 issupported on its opposite sides from the wall of chamber 35 between thepulleys l5 and I6 and below the belt l4 so as to receive liquid whichdrains therethrough. The drained liquid containing the asphaltconstituents is withdrawn from pan [8 via conduit l9 to the asphaltreceiver 32. Entrained solid fines may be removed from the bottom ofreceiver 32 by means of outlet 33 and asphalt may be withdrawn viaconduit 34 to pump 36. The asphalt containing liquid then may beentirely pumped from the system via conduits 31 and 38 or in partrecycled via conduits 31 and 39 to inlet manifold l0 feeding thedeasphaltlng chamber.

In some operations such recycling is desirable in order to reduce the'amount of oily material in the finally discarded asphalt constituents toa minimum.

The contact material is carried along on belt M in the direction of theflow arrows and the contact material from which most of the unsorbedliquid has been separated by draining is discharged from the belt I4into the washing chamber 40. The chamber 40 communicates on its lowerend with the boot section of a bucket elevator 43. In elevator 43buckets 44 hav n perforated bottoms are moved upwardly and downwardly onendless chain 45 so as to transfer the washed contact material from theelevator boot section upwardly to duct 350 feeding supply hopper 43which in turn feeds the hydrocarbon convertor 41. The bottoms of theelevator buckets 44 are perforated, the perforations being, of such sizeas to retain the contact material particles while permitting liquid topass therethrough. The elevator casing is inclined and the buckets areso shaped that liquid which drains from any given upwardly moving bucketdoes not fall into the bucket moving upwardly therebelow, but isdelivered back to the elevator boot' section. A suitable washing solventsuch as a naphtha, kerosene, benzol or light gas oil fraction may beintroduced from an outside source through conduit 42 into conduit 48through which it passes into the elevator boot section. The solventpasses from the elevator boot section into the lower section of chamber40 via passage 49 and then passes upwardly through the washing chamberto be withdrawn from the upper portion thereof through conduit 50 to aWashing solvent receiver 5|. Baflles 52 provide a zig-zag passage inchamber 40 through which the contact material passes as it descendsthrough the bath of upwardly moving washing solvent. The solid particlesare in this manner subjected to a quick wash under conditions socontrolled as to accomplish the removal of asphalt containing liquidadhering to the outer surfaces of the contact material particles withoutsubstantial separation of the sorbed oily constituents from the contactmaterial. A relatively small amount of washing solvent may also besorbed by the contact material during the washing operation. The washedcontact material may thus contain a substantial amount of sorbed oilyconstituents from the original feed, a relatively small amount ofwashing solvent (and in some casespractically no washing solvent) and insome instances small amounts of asphalt constituents from the feed. Itshould be understood that while the gel type contact material particlesof the type described have the unusual characteristic of sorbing oilyconstituents rather than asphalt constituents from high boiling feeds,nevertheless, in the case of some feed fractions the gel type catalystwill also sorb relatively small amounts of asphalt materials. It hasbeen found that this relatively small amount of sorbed asphalticmaterials will not increase the coke deposits on the catalyst toprohibitive levels. It should be understood that in claiming thisinvention in the expressions while leaving the asphalt constituentssubstantially unsorbed"; or contact material suitable for sorbingsubstantially only the oily constituents of the liquid feed and in likeexpressions the 1 word substantially is intended to allow for theserelatively small amounts of asphalt constituents which may in someoperations be sorbed along with the much larger amount of oilyconstituents in the contact material pores.

The washed contact material bearing sorbed oily constituents may bepassed from the convertor supply hopper converter 41 as a substantiallycompact, elongated gravity feed leg flowing downwardly in conduit 55.Within the upper section of convertor 41 a horizontal partition 55 ispositioned so as to define a seal chamber 51 in the upper end of theconverter. It is into this seal chamber 51 that the contact materialfeed is delivered.

A suitable inert seal gas such as steam or flue gas may be introducedinto seal chamber 51 at a rate suflicient to maintain a gaseous pressuretherein above that in the conversion section of 46' into the upper endof l space above the moving bed sorbent in the lower portion of thedrain chamber. The partition 13 extends horizontally entirely acrosschamber 10 thereby providing a purge zone I50. A'

purge gas inlet pipe 18 connects into the top 14 above the space 15. Asorbent discharge pipe 82 connects into the lower end of purge zone I50preferably a substantial distance above the plate from manifold 65.

vessel 41. Conduit I30, diaphragm valve I3I and differential pressurecontrol instrument I82 are provided for this purpose. A plurality ofuniiormly spaced vertical conduits 58 serve as a passage for solid flowfrom seal chamber 51 onto the column 59 of contact material maintainedin a lower section of the converter. A horizontal liquid distributingplate 80 is positioned across the vessel 41 shortly above the lower endsof pipes 58. The plate 60 has therein a plurality of uniformly spacedorifices GI which are of smaller diameter than the sorbent particles butof sui'flcient size to permit flow of liquid therethrough. Two headerpipes 62 and 53 closed on one end thereof extend across the space 64between pipes 58 and substantially above the plate 80. These pipesconnect outside the vessel into heat exchange fluid inlet manifold 55and have a number of nozzles 66 spaced along their length for deliveryof liquid into the space 64 above plate 50. The liquid supplied fromnozzles 56 passes through the orifices 6i and percolates down throughthe column 59. The rate of liquid heat exchange fluid supply is limitedso as to maintain the column 59 in a non-flooded condition. The rate ofliquid heat exchange fluid supply may be so limited either by properdesign oi the number and size of the orifices GI or by throttling atvalve 61 on manifold 65. A pertition 58 is provided across the lowersection of convertor 41 and a plurality of uniformly distributed pipes69 depend from partition 68 for delivery of the used contact materialand liquid heat exchange fluid into the drain chamber 10. The partition68 is so shaped as to provide funnel shaped approach passages to each ofthe pipes 89 so as to avoid pockets of stationary solid material. Thepipes 69 are of substantial length so as to provide a gas-soliddisengaging space 85 above the bed of solids in the drain section. A gasoutlet 85 connects into the vessel so as to communicate with space 85.The drain chamber 10 is of expanded cross-sectional dimension and isprovided with a perforated bottom plate 1i which extends across chamber10 at a slope greater than about 35 degrees. The top 14 of chamber 10 issubstantially parallel to the plate 1|. While the vessel 41 above thedrain chamber 10 may be of circular or rectangular cross-sectionalhorizontal shape, the passage for solid flow along plate 1i as seenalong line 2-4 should be preferably of rectangular shape. The orifices12 in plate 1! are of suflicient size to permit the liquid heat exchangefluid to drain freely therethrough but of insuflicient size to permitpassage of sorbent particles therethrough. A vertical plate partition 13depends from the top 14 of chamber 10 and terminates at a level abovethe plate 1I so as to provide a gas distributing 1I. Below the plate 1Ithere is provided a closed sump chamber 80 having a bottom outlet 8I.

In operation relatively cool contact material bearing sorbed oilyconstituents at a temperature of the order of 400600 F., for example, issupplied onto column 59. A suitable hot liquid heat exchange fluid issupplied into space 64 The heat exchange fluid exists at a temperaturesubstantially above the desired hydrocarbon conversion temperature andits rate and temperature of supply are so controlled as to heat thesorbent to and maintain it within a suitable narrow range of hydrocarbonconversion temperatures. For example, molten lead may pass downwardlythrough orifices BI onto column 59 at a temperature of about 1050" F.and at a rate suiflcient to control a temperature of about 830 F. at thelevel of conversion zone drain pipes 89. The rate of lead flow iscontrolled below that which will flood the voids in the column 59 so asto leave adequate space for flow of liberated gaseous hydrocarbonproducts down through the column. The lead, sorbent and gaseousconversion products all pass through pipes 69 at the lower end of theconversion zone. The gaseous products are disengaged from the solidsorbent and liquid heat exchange fluid in space 85 and are withdrawn viapipe 88 to a suitable product recovery system 81 which may be ofconventional type in the industry. In connection with the gaseousproducts it will be understood that the word "gaseous" as used herein indescribing and in claiming this invention is intended in the sense ofcovering materials which are in the gaseous phase under the particularoperating conditions involved regardless of the normal'phase of thosematerials under atmospheric conditions. For example, gaseous conversionproducts leaving the convertor through circuit 86 at a temperature ofthe order of 800 F. to 950 F. and say 10 pounds gauge pressure may existsubstantially entirely in the gaseous phase under these conditionsalthough gasoline, gas oil and heavy fuel oil constituents maybe presentwhich are ordinarily liquids under atmospheric conditions. In drainsection 10, the liquid heat exchange fluid settles from the bed ofsorbent and passes through orifices 12 into sump 80. The sorbent ispurged free of any residual gaseous hydrocarbons or liquid heat exchangefluid by the introduction of a suitable purge gas such as steam or fluegas via pipe 16. The purge gas passes down through the bed of sorbentand through orifices 12 and is removed from the upper portion of sumpvia pipe 88. A suitable balile 89 may be provided to prevent entrainmentof liquid heat exchange fluid in the effluent purge gas stream. A bodyof liquid 90 is maintained within the bottom of sump 80 so as to preventescape of gas through the heat exchange fluid outlet M. The purgedsorbent passes via pipe 82 to conveyor by which it is transferred toduct 96 supplying the regenerator catalyst surge hopper 98. The rate ofsorbent withdrawal from the purge zone I50 is controlled by a suitableflow control valve I02 on pipe 82. Lead now existing at a temperature ofthe order 11 of 825 F., for example, is pumped by pump 9| through pipe92 to a heat exchanger I30 where it is again heated. The heated lead maypass via pipes I33, I34, I35 and 65 back to the convertor 41, or it maypass via pipes I33 and I36 to heater I31 wherein its temperature isfurther raised before it passes to the convertor via pipes I44 and 65.Alternately, the exchanger I30 may be bypassed entirely in which casethe lead passes via pipes 92, I39, I34 and I36 to heater I31 and thenvia pipes HI and 65 to convertor 4'I. Valves are provided on the abovepipes to permit control of the lead flow in the manner described.

The used contact material which is supplied to the regenerator surgechamber 98 has lost a substantial part of its catalytic eifectivenessdue to the deposition of a carbonaceous contaminant thereon. Theregenerator shown in the drawing is of the multi-stage variety which isdescribed and claimed in application Serial Number 447,432, filed in theUnited States Patent Oifice June 17, 1942, now Patent No. 2,417,399, andapplication Serial Number 447,433, filed in the United States PatentOfilce June 17, 1942,

nowPatent No. 2,436,780, in which applications the present applicant isone of the applicants. In general the regenerator 91 is divided into avertical series of alternating burning and cooling stages. Separategasinlets 99, I00, IM and I02 and separate gas outlets I04-I0I inclusivespaced vertically from the inlets, are provided for the burning stages.The gas inlets are supplied by a combustion supporting gas such asoxygen, air or mixtures of air and flue gas, from inlet manifold I08.Flue gas passes from the burning stages through outlets I04-I0I and ismanifolded into outlet flue I09. Heat transfer tubes or coils may besuitably spaced within the cooling stages. Pipes II are inlets to thesetubes and pipes III are outlets therefrom. The inlet pipes II 0 connectinto an inlet manifold H2 and the outlet pipes connect into an outletmanifold H3. The hot heat exchange fluid from manifold II3 passes viapipe I I4 to heat exchanger I30 wherein it gives up its heat to thefluid entering via pipe 92. For example, heat exchange fluid from theregenerator existing at about 1050 F. may be cooledin exchanger I30 toabout 830 F. The cooled fluid passes via pipe I45 to a cooler I46wherein it is further cooled before passing via pipe I41, pump II! andpipe II8. back to the inlet manifold II2. In this manner a large por- 12in hopper 43 through conduit I0. The heat recovered from the finalcooling ofthe regenerated contact material may thereby be utilized forpartially heating the cooler, oily constituent bearing contact materialin hopper 40. The heat exchange fluid, relieved of its heat in hopper 40may be withdrawn from the tubes therein through conduit 1| andreintroduced into the tubes in hopper 29 through conduit 99. A pump tionof the heat liberated on regenerating the sorbent material may be usedfor heating the sorbent within the convertor 41. The regenerator heatexchange fluid may take any of a number of .forms such as a suitable gasunder pressure or fused metallic oxides or mixtures of certain fusedinorganic salts.

Hot regenerated contact material is withdrawn from the lower end ofregenerator 91 through outlet H9 at the desired rate as controlled bythrottle valve I20. The hot regenerated contact material is thentransferred by conveyor I2I to hopper 29 where it is cooled to atemperature at which it may be reused in the deasphalting operation. Theregenerated contact material in hopper 29 is cooled to a temperaturesuitable for its introduction into deasphalting chamber 20 by means of asuitable heat exchange fluid introduced at 68 and removed at 59. Ifdesired, heat transfer tubes may be provided in both hoppers 29 and 46;and the heat exchange fluid withdrawn from the heat transfer tubes inhopper 29 via conduit 69 may be introduced into the tubes I2 may beprovided to cyclically circulate the heat exchange fluid and anexchanger I3 may be provided to permit any heat adjustments that may -berequired by the desired contact material outlet temperatures fromhoppers 29 and 40. Heat may either. be added or withdrawn by means ofexchanger I3 as the particular operation involved requires;

While the system described hereinabove is one of the preferred forms ofthis invention. it should be understood that the various elements makingup the particular combined system described are shown in highlydiagrammatic form in the drawing and that'the invention is not intendedto be limited to the par icular detailed construction of the variouselem nts as shown. For example, while it is preferre to percolate theliquid charge downwardly throug a column of the gel particles in thedeasphalting chamber, nevertheless it is contemplated that within thescope of this invention the contacting of the gel particles and theliquid charge may be accomplished in a number of other ways and anymethod which permits the desired contacting is considered to be withinthe scope of this invention. For example, the liquid charge and the gelparticles might be merely charged to a batch type mixer provided withsuitable mechanical mixing devices and after suitable mixing has beenaccomplished, the material may then be discharged from the mixer to asuitable liquid solid separator. Likewise other methods and apparatusthan that described hereinabove may be employed to effect separation ofunsorbed liquid material from the contact material bearing sorbed oilyconstituents.

For example, a rotary type filter provided with suitable means foraccomplishing both filtering oil of unsorbed liquid and washing of thecontact material may be employed. In some operations the washing stepmay be eliminated entirely and the combination of draining and purgingof the contact material with a suitable purging gas may be relied uponto separate the contact material from unsorbed asphalt containingliquid. Moreover, while in the system described he einabove the washedcontact material was partially heated and then charged through a gravityfeed leg to the converter, it is contemplated that the preliminarypartial heating step may be eliminated and all of the heatingaccomplished within the convertor. Also suitable forced feed devices maybe substituted for the gravity feed leg in less preferred forms of theinvention as means of introducing the contact material bearing sorbedoily constituents into the convertor. It is also contemplated that theconvertor and regenerator construction may be materially different fromthat shown in the drawing. Other suitable means for disengagement ofgaseous products from the solid sorbent and the liquid heat exchangefluid may be employed. Also means other than that shown may be providedforaccomplishing the separation of the heat exchange liquid from theused solid sorbent as will be apparent to those skilled in the art. Theregenerator may be of the single stage type or of tical and desirable inorder to prevent undue attrition of the contact material to handle thecontact material as a substantially compact moving bed or column in theconvertor and regenerator and to convey it between vessels by continuousbucket elevators. However, within the broader scope of this invention itis contemplated that the contact material may move in suspension in theliquid heat exchange fluid in the heating and conversion zone and in thegaseous regeneration agent in the regeneration zone; and that meansother'than bucket elevators may be employed for transferring the contactmaterial irom one zone to another. It is further contemplated thatwithin its broader scope the method of this invention may involve asubstantially in situ process wherein the contact material remainspermanently in one or more vessels. For example, the deasphalting,draining, washing, heating conversion and catalyst regeneration andcooling steps may be conducted in proper cycle in a single chamber inwhich the contact material particles remain as a fixed bed. In the caseof operation of the latter type the contact material is heated bypercolating a hot liquid heat exchange fluid through the fixed bed ofsorbent bearing oily constituents until the desired conversion of thehydrocarbons has occurred. Thereafter the bed is purged substantiallyfree of heat exchange fluid and a stream of air is passed through thebed to accomplish the regeneration. If desired a liquid heat exchangefluid may be percolated through the fixed bed during regeneration toremove the liberated heat. After the regeneration a separate heatexchange liquid may be percolated through the bed to cool it to asuitable temperature for the deasphalting step. Such an in situoperation may be conducted in a battery of side by side vesselscontaining fixed sorbent beds. The operation of the several vessels maybe regulated so that a different step of the cyclic operation is beingconducted in each vessel at any given time. The heat exchange fluidpassing from a vessel in which the catalyst is being regenerated may bepassed through the catalyst bed in a vessel in which the heating step isin progress, and from the latter vessel the heat exchange fluid mayreturn to the bed undergoing regeneration. A batch type operationwherein the contact material is moved periodically, batch-wise from zoneto zone is also contemplated.

It will be understood that the desirable conditions of operation duringthe deasphalting, washing, conversion and catalyst regeneration andcooling steps will vary depending upon the particular liquid chargestock involved and the conversion reaction involved and the particularconversion products desired. Certain general conditions of operationmust, however, be observed.

' temperature.

14 decreases. The desirable sorption temperature has been found to varfrom below room temperature to about 500 F. depending on the liquidtraction treated. The temperature of the hydrocarbon liquid charged intothe sorption zone and the contact material supplied thereinto should beboth adjusted to provide the desired sorption The contact materialshould not be permitted to contact the-asphalt containing liquid feed attemperature at which substantial thermal coking of the liquid fractionwould take place. This means that in general the contact material shouldbe cooled in hopper 29 of Figure 1 for'example, to a temperature whichis at least below about 750 F. The pressure in the sorption zone mayconveniently be within the order of atmospheric to 50 pounds per squareinch. The residence time of the contact material within section 28 ofchamber 20, i. e. the sorption zone,

may vary from about l-l0 hours depending upon the liquid fractioninvolved, the temperature and the ratio of the contact material to theliquid charge. .In many operations it is desirable to control theresidence time of the contact material in chamber 20 by means of valve3| such as will permit substantial saturation of the contact materialwith sorbed oily constituents.

The ratio of contact material to liquid charge to the deasphaltingchamber may vary from about 0.5 to 20 parts by weight of contactmaterial per part of liquid asphalt bearing charge and preferably fromabout 2 to 6 parts of contact material per part of liquid charge.

The amount of solvent employed in the washing operation may varydepending upon the characteristics of the solvent and of the 'unsorbedliquid involved. In general the contact material washing should be arelatively quick wash so controlled as to prevent removal by the solventof substantial amounts of sorbed oily constituents from the contactmaterial. The amount of solvent employed may be of the order of 0.25 to2.0 volumes of solvent per volume of contact material. In someoperations the purging step following the washing step may be omittedbut when this step is employed the purging gas employed should be a gaswhich is not apt to cause oxidation of the oily constituents during theconversion, unless of course, the conversion process in-, volved is apartial oxidation process. Steam, nitrogen, flue gas and low molecularweight hydrocarbon gases are suitable purging gases for most operations.

As an example of the separation obtainable in the deasphalting step ofthis process, the treatment of an East Texas crude bottoms fractionhaving an A. P. I. gravity of 15.0 at 60 F., a Saybolt Universalviscosity of 512 seconds at 210 F., a pour point above F., and aConradson carbon residue of 11.1 percent may be considered.

The vacuum assay distillation of this feed fraction was as follows:

F. I, B. P 880 10% 964 30% 1026 40% 1054 47% 1082 This feed fraction wascontacted in a suitable confined chamber with a silica-alumina,spheroidal gel catalyst prepared by the method described in UnitedStates Patent 2,384,946 issued September 18, 1945 to Milton Marisic. Thecatalyst unpacked density was about 44 pounds per in the range 4 to 16mesh by Tyler standard screen analysis. The catalyst had beenregenerated until the residual carbon thereon was below 0.5% by weight.During the operation the temperature was maintained at about 275 F. andthe pressure was substantially atmospheric. The ratio of liquid tocatalyst charge to the sorption zone was about 332 parts by weight ofcatalyst per part by weight of liquid charge. The

residence time within the sorption zone was about 240 minutes. Theunsorbed liquid was recycled until substantially all of the oilyconstituents had been removed therefrom. Finally a tar fractionamounting to about 30 percent by weight oi the liquid charge wasseparated from the catalyst bearing sorbed oily constituents and thecatalyst was washed with about half of its weight oi Stoddard solvent,the residence time of the catalyst in the washing operation beinglimited to about 3 minutes. The catalyst after washing contained about22 percent of its original weight of sorbed oily constituents whichrepresented about 70 percent by weight of the original liquid charge.The catalyst bearing oily constituents was then heated to a temperaturesuitable for the cracking conversion oi the sorbed oilyconstituents in aconfined conversion zone. An an-' alysis of the sorbed oilyconstituentsbefore conversion was as' follows: A. P. I. gravity 17.1; viscosity (K.V.) at 210 F.-46; pour point above 120 F., and Conradson carbon residue5.7% by weight,

When the contact material bearing sorbed oily constituents is partiallyheated before introductionto the conversion zone as shown in Figure 1,it should be heated only to a temperature which is substantially belowthe desired conversion temperature. Usually a temperature of the orderof 750 F. is the maximum temperature to which the contact materialshould be heated in hopper 46 of Figure 1. As has been pointed out, thecontact material introduced to chamber 20 should be below about 750 F.so that regenerated contact material in hopper 29 of Figure 1 should becooled to a level at least below about 750 F.

The operating conditions within the converter M will vary depending uponthe activity of the catalyst employed, the particular petroleum chargeinvolved, the reaction involved and the products desired. In general ithas been found desirable to maintain the pressures within av rangevarying from sub-atmospheric to about 200 pounds per square inch.Pressures of the order of to 50 pounds per square inch gauge arepreierred. The temperature for the conversion for cracking operationsmay vary from about 750 F. to 1100 F., temperatures of the order of 850to 1000 F. being preferred where gasoline is the desired product. Wherenoncondensable gases are the principal desired product somewhathigher-temperatures may be employed. The ratio of contact material tohydrocarbon throughput may vary from about 1.0 to 40 parts by weight ofcontact material per part of hydrocarbon charge.

The rate of liquid heat exchange fluid charge to the conversion zonewillvary dependent upon the heat requirements of the particular operationinvolved. As an example, in the catalytic cracking of hydrocarbons aninorganic oxide gel catalyst having a density of about 40 pounds percubic foot may be employed. The reaction temperature may be of the orderof 8501000 F. with the catalyst entering the conversion zone at fromsaid contact material and said liquid heat about 400 F.'carrying about30 percent by weight sorbed oil and'leaving the conversion zone at.

about 850 F. Lead may be percolated through the catalyst bed at a ratewithin the range about 20 to pounds of lead per pound oi catalystthroughput, for lead supply temperatures of the order of 1200-950 F.respectively.

In the contact material regenerator, pressure of the orderof.atmospheric to about pounds per square inch may be employed,pressures around atmospheric being preferred. The contact materialtemperature should be controlled below a heat damaging level by removalof heat therefrom during the course of the contaminant burning. The heatdamaging level is that level at. which and above which the contactmaterial suflers permanent loss in catalytic effectiveness for theconversion involved or loss in sorptive efliciency. The heat damagingtemperature may vary from temperatures above about 1150" F. totemperatures above about 1450" F. depending upon the particular gel typecatalyst involved.

It should be understood that the details of apparatus construction andarrangement, of operating conditions, and of applications of the processof this invention given herelnabove are intended merely as illustrativeand it is not intended that the scope of this invention should belimited thereto or limited otherwise except as it may be limited in thefollowing claims.

I claim:

-1. A process for conversion of oily constituents in asphalt bearinghydrocarbon liquid feeds which comprises: contacting the hydrocarbonfeed with a suitable solid sorbentmaterial for sorbing the oilyconstituents, said sorbent being one in which more than about '70percent of 'its pores are micropores, controlling the size of thesorbent particles and the contact time and temperature and the relativeamounts of liquid and sorbent contacted to effect sorption of the oilyconstituents into the pores of said sorbent while leaving substantiallyunsorbed the asphalt constituents, the size of sorbent particlesemployed being larger for longer contact periods and higher contacttemperatures, separating the sorbent bearing sorbed oily constituentsfrom the unsorbed asphalt constituents, and contacting said sorbentdirectly with a hot liquid non-wetting heat exchange fluid to heat saidsorbent to a temperature suitable for the desired conversion of the oilyconstituents.

2. A process for conversion of high boilin oily constituents in asphaltbearing hydrocarbon fractions to lower boiling products which comprises:contacting said liquid fraction for a suitable time and at a suitabletemperature with a porous solid contact material in which the particlesize is greater than about 60 mesh size and in which most of the poresare micropores and the volume of pores having radii larger than about100 Angstrom units is less than about 30 percent of the total porevolume to effect the sorption of the oily constituents of said feed inthe pores of said contact material while leaving the asphaltconstituents substantially'unsorbed; effecting a substantial separationof the unsorbed liquid from the contact material which bears the sorbedoily constituents, and passing a suitable hot, nonwetting liquid heatexchange medium into direct contact with said contact material to heatit to a temperature suitable for conversion of said sorbed oilyconstituents to lower boiling products, separating the lower boilinghydrocarbon products 17 exchange medium. separating said liquid heatexchange medium from said contact material, reheating said heat exchangemedium and again passing it into contact with contact material bearingsorbed oily constituents.

3. A process for the conversion of the oily constituents of high boilingliquid asphalt containing hydrocarbon feeds which comprises: contactingsaid liquid feed for a suitable time and a suitable temperature for oilyconstituent sorption with a porous particle-form inorganic oxidegel-type contact material in which most of the pores are micropores andthe volume of pores having rdii larger than about 100 Angstrom units isless than about 30 percent of the total pore volume and in which theparticles are greater than about 30 mesh size, to effect the sorption ofthe oily constituents of said feed in the pores oi said contact materialwhile leaving the asphalt constituents substantially unsorbed; eflectingseparation of the non-sorbed asphalt containing liquid from said contactmaterial containing sorbed oily constituents, passing said contactmaterial containing sorbed oily constituents through a confinedconversion zone in admixture with a sufllcient amount of hot liquid heatexchange fluid to heat it to a temperature suitable for the desiredconversion of said sorbed oily constituents, said liquid heat exchangefluid being incapable of substantially wetting said contact material,separating converted hydrocarbon fluid products from said contactmaterial and liquid heat exchange fluid, separating the used contactmaterial from said liquid heat exchange fluid, passing said used contactmaterial through a confined regeneration zone while contacting it withan oxygen containing gas to burn off contaminant deposits and therebyregenerate said contact material, cooling the regenerated contactmaterial to a temperature suitable for its use in contacting saidasphalt bearing liquid feed and reusing the cooled contact material forcontacting asphalt bearing liquid feed as aforesaid, heating the liquidheat exchange fluid after its separation irom said used contact materialand returning the heated liquid heat exchange fluid to said conversionzone to heat said contact material as aforesaid.

4. A process for conversion of high boiling oily constituents in asphaltbearing hydrocarbon fractions to lower boiling products which comprises:contacting said liquid fraction with a porous particle form inorganicoxide gel-type catalyst in which most of the pores are micropores andthe volume of pores having radii larger than about 100 Angstrom units isless than about 30 percent and in which the particles are greater thanabout .022 inch average diameter to efl'ect sorption of the oilyconstituents of said fraction in the pores of said catalyst whileleaving the asphalt constituents substantially unsorbed, efiectingseparation of said catalyst bearing sorbed oily constituents from thenon-sorbed asphalt version zone, separating the liquid heat exchange amedium from the used catalyst upon which a carbonaceous contaminant hasbeen deposited, passing the used catalyst through a confinedregeneration zone while contacting it with a combustion supporting gasto burn off said carbonaconstituents, passing said catalystbearingIsorbed ceous contaminant, controlling the temperature of saidcatalyst below a heat damaging level in said regeneration zone, coolingthe regenerated catalyst to a temperature suitable for its use incontacting said asphalt bearing liquid fraction,

re-using the cooled catalyst for contacting said asphalt bearing liquidas aforesaid, heating the liquid heat exchange medium after itsseparation from said used catalyst to a temperature substantially abovethe desired hydrocarbon conversion temperature and returning said heatedliquid heat exchange medium to said conversion zone.

5. A process for conversion of the oily constituents present in a liquidhydrocarbon feed stock containing both oily and asphaltic constituentsat elevated temperatures in the presence of a particle-form contact massmaterial which process comprises: contacting the liquid charging stockin a confined deasphalting zone with a particle-form porous contactmaterial having the pore structure of an inorganic oxide gel in whichthe total pore volume is taken up mostly by micropores, there being lessthan about 30 percent pores having radii larger than about Angstromunits, the contact material being made up substantially of particleslarger than about 30 mesh size; controlling the temperature during thecontacting at a level suitable for the sorption of oily constituents inthe pores of the contact material and below that which would causesubstantial coking of the asphalt constituents, which constituentsremain substantially unsorbed in the pores of said contact material;eflecting separation of the contact material bearing sorbed oilyconstituents from the unsorbed constituents of said hydrocarbon feedstock; passing the separated contact material bearing sorbed oilyconstituents downwardly as a substantially compact column through anelongated, confined substantially vertical conversion zone to eflectconversion of said oily constituents to lower boiling gaseous products;passing a hot liquid heat exchange medium downwardly through said columnat a rate below that which would flood the voids in said column, saidheat exchange medium being incapable of substantially wetting saidcontact material, controlling the supply rate and temperature of saidliquid heat exchange medium to effect heating of said contact materialto a temperure suitable for said hydrocarbon conversion, separating thegaseous products from said contact material and liquid heat exchangefluid, separating the used contact material upon which a carbonaceousdeposit has formed from the liquid heat exchange fluid, passing the usedcontactmaterial through a confined regeneration zone while contacting itwith an oxygen containing gas to burn oil said carbonaceouscontaminants, passing a second fluid heat exchange medium in heatexchange relationship with said contact material in said regenerationzone to remove the heat liberated by said contaminant burning, efiectingan exchange of heat from said'second heat exchange medium to said firstheat exchange medium which has been separated from said used contactmaterial, thereby heating said first heat exchange medium to atemperature substantially above the average conversion temperature insaid conversion zone, returning said first heat exchange medium to 8. Aprocess for conversion oi high boiling oily constituents in asphaltbearing hydrocarbon fractions to lower boiling products which comprises:contacting said liquid fraction with a porous particle form inorganicoxide gel-type catalyst in which most of the pores are micropores andthe volume of pores having radii larger than about 100 Angstrom units isless than about 30 percent and in which the particles are greater thanabout .022 inch average diameter to effect sorption of the oilyconstituents of said fraction in the pores of said catalyst whileleaving the asphalt constituents substantially unsorbed, eflfectingseparation of said catalyst bearing sorbed oily constituents from thenon-sorbed asphalt constituents, passing said catalyst bearing sorbedoily constituents downwardly through a confined conversion zone as asubstantially compact column, introducing a molten metal heat exchangemedium into the upper section of said conversion zone at a temperaturesubstantially above the desired average hydrocarbon conversiontemperature, percolating saidheat exchange medium downwardly throughsaid column at a rate sufficient to heat it to a temperature suitablefor conversion of said oily constituents to lower boiling gaseousproducts, and withdrawing the gaseous products, used catalyst and heatexchange medium from the lower section of said conversion zone.

7. A process for conversion of high boiling oily constituents in asphaltbearing hydrocarbon fractions to lower boiling products which comprises:contacting said liquid fraction with a porous particle form inorganicoxide gel-type catalyst in which most of the pores are micropores andthe volume of pores having radii larger than about 100 Angstrom units isless than obout 30 percent and in which the particles are greater thanabout .022 inch average diameter to effect sorption of the oilyconstituents of said fraction in the pores of said catalyst whileleaving the asphalt constituents substantially unsorbed, effectinseparation of said catalyst bearing sorbed oily constituents from thenon-sorbed asphalt constituents, passing said catalyst bearing sorbedoily constituents downwardly through a confined conversion zone as asubstantially compact column, passing a hot liquid heat exchange mediumdownwardly through said column at a rate insuflicient to flood the voidsin said column but at a temperature and rate sufficient to heat saidcatalyst to a temperature suitable for conversion of said oilyconstituents to lower boiling gaseous products, said heat exchange fluidbeing incapable of substantially wetting said catalyst, withdrawing theused catalyst, gaseous products and liquid heat exchange medium from thelower section of said 20 conversion zone, separating said gaseousproducts from the catalyst and liquid heat exchange medium, draining theliquid heat exchange medium from said catalyst and finally purging saidcatalyst with a suitable inert purge gas, passing the purged catalystthrough a confined regeneration zone while contacting it with an oxygencontaining gas to burn off from the catalyst carbonaceous contaminantsdeposited thereon in said conversion zone, cooling the regeneratedcatalyst to a temperature suitable for its use in sorbing oilyconstituents and re-using the cooled catalyst for above the averagehydrocarbon conversion temperature in said conversion zone and returningthe heated heat exchange medium to the upper section of said conversionzone.

8. A process for conversion of oily constituents in asphalt bearinghydrocarbon liquid feeds which comprises: contacting the hydrocarbonfeed with a porous, particle form solid sorbent in which most of thepores are micropores and the volume of pores having radii larger thanabout Angstrom units is less than 30 percent of the total pore volumeand having an average particle diameter greater than that correspondingto about 60 mesh Tyler, controlling the contact time and temperature andthe relative amounts of liquid and sorbent contacted to eflect sorptionof the oily constituents into the pores of said sorbent while leavingsubstantially unsorbed the asphalt constituents, separating the sorbentbearing sorbed oily constituents from the unsorbed asphalt constituents,and passing a hot preheated molten metal directly into contact with saidcontact material to heat it to a temperature suitable for the desiredconversion of said sorbed oily constituents.

LOUIS P. EVANS.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PA'I'ENTS Number Name Date 226,001 Reibeck Mar. 30, 18801,278,023 Rosenbaum Sept. 3, 1918 1,447,297 Day Mar. 6, 1923 1,568,018Forrest et al Dec. 29, 1925 2,354,354 Abrams July 25, 1944 2,354,355Abrams et a1 July 25, 1944 2,382,755 Tyson Aug. 14, 1945 2,437,222Crowley, Jr., et al. Mar. 3, 1948 OTHER REFERENCES Allibone: Journal ofthe Institute of Petroleum," vol. 2'7, pages 94-108 (1941).

